CN115404289B - Reactive fatting agent and preparation method thereof - Google Patents
Reactive fatting agent and preparation method thereof Download PDFInfo
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- CN115404289B CN115404289B CN202210963034.5A CN202210963034A CN115404289B CN 115404289 B CN115404289 B CN 115404289B CN 202210963034 A CN202210963034 A CN 202210963034A CN 115404289 B CN115404289 B CN 115404289B
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- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
- C14C9/02—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes using fatty or oily materials, e.g. fat liquoring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/04—Formation of amino groups in compounds containing carboxyl groups
- C07C227/06—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid
- C07C227/08—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid by reaction of ammonia or amines with acids containing functional groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
- C07C227/16—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions not involving the amino or carboxyl groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
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Abstract
The invention belongs to the field of tanning chemical industry, and discloses a reactive fatting agent and a preparation method thereof. According to the preparation method, epoxidized soybean oil is used as a raw material, firstly, the epoxidized soybean oil is subjected to ring opening through a hydroxyl compound, then the epoxidized soybean oil is reacted with epoxy chloropropane to prepare end-chloro triglyceride, and finally, the end-chloro triglyceride and an emulsifier are compounded to obtain the reactive type fatting agent based on the epoxidized soybean oil. In the process of fatting, chlorine atoms in the fatting agent can react with amino groups on the collagen fibers so as to be combined with the collagen fibers. The combination mode is firmer than the combination mode of the common anionic fatting agent and the electrovalence of the collagen fiber, can endow the fatting agent with better combination property and migration resistance, and is simultaneously suitable for chrome tanning and chrome-free tanning systems with weaker positive electricity.
Description
Technical Field
The invention relates to the field of tanning chemical industry, in particular to a reactive fatting agent and a preparation method thereof.
Background
The fatting is one of the important procedures in the leather production process, and the fatting can wrap the grease on the surface of the collagen fibers through the physical and chemical actions, and forms a layer of oil film with lubricating action among the collagen fibers, so that the softness, fullness and elasticity of leather are improved, and the tensile strength and tearing strength of the leather are improved.
The fatting agent is one of core materials used in the fatting process, and mainly comprises a grease component and an emulsifier component. The common grease components in the conventional fatting agent are mainly natural animal and vegetable grease such as fish oil, lard, modified vegetable oil, castor oil and the like, and the grease has good fatting performance, and can endow leather with good oil wettability and plumpness after being compounded with an emulsifying agent. However, the natural animal and vegetable oils often contain a large amount of unsaturated double bonds, and the double bonds are easily oxidized by air, so that phenomena such as yellowing and peculiar smell are generated in the use process of the finished leather, and the quality of the finished leather is affected. In addition, the number of polar groups in the molecular structure of the traditional natural animal and vegetable oil is small, and the traditional natural animal and vegetable oil can be combined with collagen fibers only through physical adsorption and hydrogen bonding in the process of fatting, so that oil components are easy to migrate and not resistant to water washing in the process of storing finished leather. In this case, the preparation of a novel fat liquoring agent which is resistant to yellowing, has a strong binding ability with collagen fibers and has a good storage stability by modifying natural animal and vegetable oils has been the development direction of the fat liquoring agent.
The epoxidized soybean oil is a product obtained by the epoxidation reaction of soybean oil, and has the characteristics of wide sources and environmental friendliness. Literature (Yu Yajin. Study of perovskite oxide/ZnO Quantum dot/modified epoxidized Soybean oil nanocomposite Lipozzolanic Agents [ D)]The university of technology of Shaanxi, 2020.) is used for carrying out esterification reaction on epoxidized soybean oil and maleic anhydride to synthesize soybean oil maleic acid monoester, and then sulfonic acid groups are further introduced through sulfonation reaction, so that the Gemini type modified epoxidized soybean oil fatliquor is prepared. The fatting agent not only can improve the softness and plumpness of chrome tanned leather, but also can endow the chrome tanned leather with good yellowing resistance. Notably, the sulfonic acid group is introduced in the preparation process of the fatting agent, and has stronger negative charge. In the process of fatting chrome tanned leather, the sulfonic acid group in the fatting agent can be combined with-NH in crust leather 2 、Cr 3+ And the like are combined with each other by electrostatic interaction, and thus exhibit a good migration resistance. However, for organic tanning, the combination capability of the conventional anionic fatting agent and collagen fibers is not strong and the fatting performance is limited because of weak positive electricity of crust leather.
In view of this, the present invention has been made.
Disclosure of Invention
In order to solve the problems in the background technology, the invention provides the yellowing-resistant reactive fatting agent prepared by using the epoxidized soybean oil.
In order to achieve the above purpose, the invention adopts the following scheme:
the reactive fatting agent comprises 15-45 parts of chlorine-terminated triglyceride and 2-6 parts of emulsifier by weight;
wherein, the structural formula of the end-chloro triglyceride is:
wherein R is 1 Is->
、
、/>
Any one of them.
Preferably, the end-chloro triglyceride is obtained by ring-opening epoxy soybean oil through hydroxyl-containing compound and then reacting with epoxy chloropropane.
Preferably, the hydroxyl-containing compounds include, but are not limited to, lactic acid, ethanolamine, diethanolamine.
Preferably, the weight ratio of the epoxidized soybean oil, the hydroxyl compound and the epichlorohydrin is (2-4) 1 (1-2.5).
Preferably, the epoxidized soybean oil has an epoxy value greater than 6.
Preferably, the emulsifier is selected from tween 80 and/or span 80.
The invention adopts another technical scheme that:
a method of preparing a reactive fatliquor comprising the steps of:
mixing epoxidized soybean oil and a hydroxyl-containing compound at room temperature, adding a first catalyst, heating to 80-130 ℃, and reacting for 4-8 hours to obtain an epoxidized soybean oil ring-opening product;
mixing the epoxidized soybean oil ring-opening product with epichlorohydrin at room temperature, adding a second catalyst, heating to 70-90 ℃ and reacting for 6-10 hours to obtain end-chloro triglyceride; and
and mixing the end-chloride triglyceride and the emulsifier, and stirring for 1-2 hours at 70-90 ℃.
Preferably, the first catalyst is selected from any one or more of tetrabutylammonium bromide, triphenylphosphine and zinc chloride;
the second catalyst is selected from triphenylphosphine and/or boron trifluoride diethyl etherate.
Compared with the prior art, the invention has the following beneficial effects:
according to the preparation method, epoxidized soybean oil is used as a raw material, firstly, the epoxidized soybean oil is subjected to ring opening through a hydroxyl compound, then the epoxidized soybean oil is reacted with epoxy chloropropane to prepare end-chloro triglyceride, and finally, the end-chloro triglyceride and an emulsifier are compounded to obtain the reactive type fatting agent based on the epoxidized soybean oil. In the process of fatting, chlorine atoms in the fatting agent can react with amino groups on the collagen fibers so as to be combined with the collagen fibers. The combination mode is firmer than the combination mode of the common anionic fatting agent and the electrovalence of the collagen fiber, can endow the fatting agent with better combination property and migration resistance, and is simultaneously suitable for chrome tanning and chrome-free tanning systems with weaker positive electricity.
The epoxidized soybean oil with higher saturation is used as a raw material, and unsaturated double bonds are not introduced in the reaction process, so that the product has good photo-thermal stability, and the leather after being fattened is yellowing-resistant and has no peculiar smell.
The raw materials of the fatting agent are green and environment-friendly, the product is simultaneously suitable for chrome tanning and non-chrome tanning, has the advantages of good fatting effect, high absorptivity and yellowing resistance, and provides a new way for preparing the reactive fatting agent.
Drawings
FIG. 1 is an infrared spectrum of the epoxidized soybean oil a, the product b obtained after ring opening of the epoxidized soybean oil with lactic acid and the end-chloro triglyceride c in example 1 of the present invention;
FIG. 2 shows the nuclear magnetic resonance carbon spectra of epoxidized soybean oil a and lactic acid ring-opened product b and end-chloro triglyceride c in example 1 of the present invention.
Detailed Description
The present invention will be further described in detail with reference to the following detailed description and the accompanying drawings, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the description is only illustrative and is not intended to limit the scope of the invention. In addition, in the following description, descriptions of well-known structures and techniques are omitted so as not to unnecessarily obscure the present invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The first embodiment of the invention provides a reactive fatting agent which comprises 15-45 parts by weight of end-chloride triglyceride and 2-6 parts by weight of emulsifier;
wherein, the structural formula of the end-chloro triglyceride is:
wherein R is 1 Is->
、
、/>
Any one of them.
When the fatting agent is used for fatting, chlorine atoms in the chlorine-terminated triglyceride can react with amino groups on the collagen fibers to realize the combination with the collagen fibers, and the combination mode is firmer than the mode of combining the anionic fatting agent with the electricity valence of the collagen fibers in the prior art, so that the fatting agent can be endowed with better combination property and migration resistance, and can be simultaneously applied to chrome tanning and chrome-free tanning systems with weaker positive electricity.
The end-chloro triglyceride is obtained by ring-opening epoxy soybean oil through hydroxyl-containing compound and then reacting with epoxy chloropropane.
Wherein the structural formula of the epoxidized soybean oil is
Wherein R and R' are long carbon chains and the number of carbon atoms is 5-10. />
Epoxidized soybean oil is prepared byThe structural formula of the ring-opening product after the ring opening of the hydroxyl compound is
Wherein R is 2 Is->
、/>
、/>
Any one of them.
For the selection of hydroxyl-containing compounds, the structure should be such that: the epoxy soybean oil contains hydroxyl and active functional groups which have higher reactivity with epoxy groups than hydroxyl, so that chlorine atoms can be introduced by reacting with epichlorohydrin after ring opening of the epoxy soybean oil. In some preferred embodiments, the hydroxyl-containing compounds include, but are not limited to, lactic acid, ethanolamine, diethanolamine.
The amount of each raw material is preferably such that the reaction can be sufficiently performed, and in some preferred embodiments, the weight ratio of the epoxidized soybean oil, the hydroxyl compound, and the epichlorohydrin is (2 to 4): 1 to (2.5).
In order to make the ring-opening reaction more sufficient and facilitate the subsequent reaction with epichlorohydrin to introduce more active chlorine atoms, the epoxidized soybean oil with the epoxy value of more than 6 is preferred in the embodiment of the invention.
The emulsifying agent is commonly used in the field, and the tween 80 and/or span 80 are preferred in the embodiment of the invention.
The second embodiment of the present invention provides a method for preparing a reactive fatliquor, comprising the steps of: mixing epoxidized soybean oil and a hydroxyl-containing compound at room temperature, adding a first catalyst, heating to 80-130 ℃, and reacting for 4-8 hours to obtain an epoxidized soybean oil ring-opening product;
mixing the epoxidized soybean oil ring-opening product with epichlorohydrin at room temperature, adding a second catalyst, heating to 70-90 ℃ and reacting for 6-10 hours to obtain end-chloro triglyceride; and
and mixing the end-chloride triglyceride and the emulsifier, and stirring for 1-2 hours at 70-90 ℃.
The first catalyst is selected from any one or more of tetrabutylammonium bromide, triphenylphosphine and zinc chloride;
the second catalyst is selected from triphenylphosphine and/or boron trifluoride diethyl etherate.
In order to better understand the technical scheme provided by the invention, the preparation method and the application performance are respectively described in the following specific examples.
The yellowing resistance, physical and mechanical properties, softness, thickness and absorptivity of the retanned crust leather mentioned in the following application examples and application comparative examples were measured by a yellowing resistance test box (GT-7035-NUAB, high-speed rail testing instruments Co., ltd.), a tensile tester (GT-AI-7000S, high-speed rail testing instruments Co., ltd.), a leather softness tester (GT-303, high-speed rail testing instruments Co., ltd.), a thickness tester (GT-313, high-speed rail testing instruments Co., ltd.) and a total organic carbon analyzer (LiquiTOC, elementar, germany), respectively.
The following application examples and comparative application examples mentioned the organic solvent resistance was determined by the following method: the crust leather was cut into 2mm X2 mm particles, and leather sample particles (mass: m 1 ) And wrapped with filter paper. Extracting the particles wrapped with filter paper with dichloromethane as solvent, taking out after 4 h, oven drying at 105deg.C to constant weight, taking out leather sample particles (mass is denoted as m) 2 ). At the same time, unextracted blank skin-like particles (mass recorded as m 3 ) Drying at 105deg.C to constant weight (mass is denoted as m) 4 ). The methylene chloride extract content ω in the leather was calculated according to the following formula. The lower the dichloromethane extract content, the better the leather is resistant to organic solvent extraction.
Example 1
Preparation of the reactive fatliquoring agent:
mixing 112.5 g lactic acid with 2.25 g tetrabutylammonium bromide and 4.5 g triphenylphosphine, adding into a three-neck flask, stirring at normal temperature for 10 min, adding 300 g epoxidized soybean oil, heating to 80 ℃ and stirring for reacting 8 h to obtain an epoxidized soybean oil ring-opening product. The above product was mixed with 7 g triphenylphosphine in a three-necked flask at room temperature, and then 210 g epichlorohydrin was added thereto, and the temperature was raised to 70℃and stirred for reaction 10 h. Taking out the product, mixing with 56 g Tween 80 at 70deg.C under stirring for 2 h to obtain the final product.
In this example, the infrared spectra of epoxidized soybean oil a, the product b obtained by ring-opening epoxidized soybean oil with lactic acid, and the end-chloro triglyceride c are shown in fig. 1, and the nmr carbon spectrum is shown in fig. 2.
Map a in FIG. 1 is at 824 cm -1 、1242 cm -1 The characteristic peak of epoxy group in the molecular structure of the epoxidized soybean oil is shown, and the peak completely disappears in the map b, so that the successful reaction of lactic acid and the epoxidized soybean oil is proved, and the epoxy group is completely opened by the carboxyl of the lactic acid. In addition, 3442 and cm in map b -1 The broad association peak at this point is a characteristic absorption peak for hydroxyl groups, which occurs due to the reaction of lactic acid and epoxidized soybean oil to form a polyol compound, and also confirms the occurrence of the ring-opening reaction of epoxy groups. Graph c end chloride triglyceride 668 cm -1 There is a C-Cl stretch vibration peak, the appearance of which confirms successful reaction of the epoxidized soybean oil polyol product with epichlorohydrin. Furthermore, 1132 and cm in FIG. c -1 The absorption peak comes from ether bond generated after hydroxy ring-opening epoxy chloropropane, and provides strong evidence for successful reaction of lactic acid ring-opening product and epoxy chloropropane.
The absorption peak of graph a at 56 ppm in FIG. 2 was derived from the carbon of the epoxy group in epoxidized soybean oil, while this peak was completely disappeared in graph b, demonstrating that lactic acid was completely reacted with epoxidized soybean oil and that the epoxy group was completely consumed. Meanwhile, absorption peaks of 62ppm and 66 ppm in the graph b are characteristic absorption peaks of carbon connected with hydroxyl groups, and successful ring opening of lactic acid and generation of a polyol compound are also confirmed. The absorption peak of 46-48 ppm in the graph c is the absorption peak of carbon connected with chlorine atoms in generated end chlorine triglyceride after the reaction of epoxidized soybean oil polyol and epoxy chloropropane, which proves that chlorine atoms are successfully introduced into the fatting agent.
Example 2
Preparation of the reactive fatliquoring agent:
mixing 55 g lactic acid with 1.25 g tetrabutylammonium bromide and 3.5 g triphenylphosphine, adding into a three-neck flask, stirring for 10 min at normal temperature, adding 200 g epoxidized soybean oil, heating to 80 ℃ and stirring for reacting 8 h to obtain an epoxidized soybean oil ring-opening product. Mixing the product with 3.5 g boron trifluoride diethyl etherate in a three-neck flask at normal temperature, adding 130 g epichlorohydrin, heating to 70 ℃, stirring to react with 6 h, taking out the product, mixing with 20 g span 80 at 80 ℃ and stirring with 1 h, thus obtaining the reactive type fatting agent based on epoxidized soybean oil.
Example 3
Preparation of the reactive fatliquoring agent:
mixing 65 g ethanolamine with 1.5 g tetrabutylammonium bromide, 1.5 g triphenylphosphine and 1.5 g zinc chloride, adding a three-neck flask, stirring for 10 min at normal temperature, adding 250 g epoxidized soybean oil, heating to 80 ℃ and stirring for reacting 6 h to obtain the epoxidized soybean oil ring-opening product. Mixing the product with 3.2 g boron trifluoride diethyl etherate in a three-neck flask at normal temperature, adding 160 g epoxy chloropropane, heating to 80 ℃, stirring to react 8 h, taking out the product, stirring and mixing the product with 43 g Tween 80 at 70 ℃ for 2 h, and obtaining the reactive type fatting agent based on epoxidized soybean oil.
Example 4
Preparation of the reactive fatliquoring agent:
mixing 100 g diethanolamine with 2.5 g zinc chloride and 4 g triphenylphosphine, adding into a three-neck flask, stirring at normal temperature for 10 min, adding 300 g epoxidized soybean oil, heating to 120 ℃ and stirring for reacting 4 h to obtain an epoxidized soybean oil ring-opening product. Mixing the product with 5 g triphenylphosphine in a three-neck flask at normal temperature, adding 160 g epichlorohydrin, heating to 70 ℃, stirring for reaction 8 h, taking out the product, and stirring and mixing the product with 32 g span 80 at 70 ℃ for 1 h to obtain the reactive type fatting agent based on epoxidized soybean oil.
Example 5
Preparation of the reactive fatliquoring agent:
mixing 135 g diethanolamine with 2 g tetrabutylammonium bromide, 2 g triphenylphosphine and 2 g zinc chloride, adding into a three-neck flask, stirring for 10 min at normal temperature, adding 300 g epoxidized soybean oil, heating to 100 ℃ and stirring for reacting 4 h to obtain the epoxidized soybean oil ring-opening product. Mixing the product with 7.5 g boron trifluoride diethyl etherate in a three-neck flask at normal temperature, adding 176 g epoxy chloropropane, heating to 90 ℃, stirring to react with 4 h, taking out the product, stirring with 60 g Tween 80 at 70 ℃ to mix with 2 h, and obtaining the reactive type fatting agent based on epoxidized soybean oil.
Application example 1
The reactive fatliquor prepared in example 1 was used in this application example to fatliquor the leather of the cow leather sofa:
the method comprises the steps of cutting the leather materials of the cow leather sofa into blue leather, putting the blue leather into a rotary drum, sequentially carrying out softening, water washing and retanning according to a conventional process, then adding 8% of reactive fatliquor and 100% of water according to the weight of the cut blue leather, rotating 1 h at 50 ℃, adding acid for fixing four times, adding 0.5% of formic acid each time, and rotating for 15 min.
The thickening rate of the wet cowhide blue skin treated by the process is 21.15 percent after fatting, the softness is 8.84 and mm, the tearing strength is 99.77 and N/mm, the absorptivity of the fatting agent is 94.26 percent, the content of dichloromethane extract is 4.98 percent, the yellowing resistance is level 4, and the grain surface is flat, fine, plump and soft.
Application example 2
This application example uses the reactive fatliquor prepared in example 3 to fatliquoring sheep garment leather:
the sheep clothing leather raw material is cut into blue leather, the blue leather is put into a rotary drum, the retuning, the washing and the retanning are sequentially carried out according to the conventional process, then 8% of reactive fatliquor and 100% of water are added according to the weight of the cut blue leather, the sheep clothing leather is rotated for 1 h at the temperature of 50 ℃, and then acid is added for fixation four times, and 0.5% of formic acid is added each time and the sheep clothing leather is rotated for 15 min.
The thickening rate of the wet sheepskin treated by the process after fatliquoring is 18.97%, the softness is 8.91 mm, the tearing strength is 83.25N/mm, the absorptivity of the fatliquoring agent is 93.35%, the content of dichloromethane extract is 5.23%, the yellowing resistance is level 4, and the sheepskin is plump and soft and has excellent comprehensive performance.
Application example 3
The reactive fatliquor prepared in example 4 was used in this application to fatliquor aldehyde tanned kraft upper leather:
the aldehyde tanned cowhide vamp leather raw material is cut into white leather, the white leather is put into a rotary drum, the retuning, the water washing and the retanning are sequentially carried out according to the conventional process, 10 percent of reactive fatliquor accounting for Bai Pipi by weight of the cut leather is added after the liquid is discharged, the mixture is rotated for 1 h at the temperature of 50 ℃, then acid is added for fixation, and 0.4 percent of formic acid is added each time and the mixture is rotated for 15 minutes.
The thickening rate of the wet cowhide white skin treated by the process is 18.84% after fatliquoring, the softness is 8.58 and mm, the tearing strength is 104.22N/mm, the absorptivity of the fatliquoring agent is 95.78%, the content of dichloromethane extract is 5.54%, the yellowing resistance level is 3.5, and the finished leather is plump and has excellent physical and mechanical properties.
Application example 4
This application example uses the reactive fatliquor prepared in example 5 to fatliquoring TWLZ tanned kraft upper leather:
the TWLZ tanned cowhide vamp leather raw material is cut into white leather, the white leather is put into a rotary drum, the retuning, the water washing and the retanning are sequentially carried out according to the conventional process, 10 percent of reactive fatliquor accounting for Bai Pipi by weight of the cut-up, 150 percent of water are added after the liquid is discharged, the mixture is rotated for 1 h at the temperature of 50 ℃, then acid is added for fixation, and 0.4 percent of formic acid is added each time and the mixture is rotated for 15 minutes.
The thickening rate of the wet cowhide white skin treated by the process is 18.41 percent after fatliquoring, the softness is 8.23 and mm, the tearing strength is 106.57N/mm, the absorptivity of the fatliquoring agent is 94.77 percent, the content of dichloromethane extract is 4.86 percent, the yellowing resistance grade is 3.5, and the finished leather is compact and has excellent physical and mechanical properties.
Comparative examples of application
The comparative example is a fatliquored kraft sofa leather with commercial rapeseed oil fatliquor:
the method comprises the steps of cutting the leather materials of the cow leather sofa into blue leather, putting the blue leather into a rotary drum, sequentially carrying out softening, water washing and retanning according to a conventional process, then adding 8% of reactive fatliquor and 100% of water according to the weight of the cut blue leather, rotating 1 h at 50 ℃, adding acid for fixing four times, adding 0.5% of formic acid each time, and rotating for 15 min.
The softness, the absorptivity of fatliquoring agent, the physical and mechanical properties, the organic solvent extraction resistance and the yellowing resistance of the finished leather obtained after fatliquoring of application example 1 and application comparative example are compared, and the results are shown in the following table:
as can be seen from the table, the leather sofa after being fattened by the reactive fatliquoring agent prepared by using the epoxidized soybean oil is similar to the commercial fatliquoring agent in softness, and the physical and mechanical properties and the absorptivity of the fatliquoring agent are better than those of the commercial fatliquoring agent, which indicates that the epoxidized soybean oil reactive fatliquoring agent prepared by the method has better fatliquoring property. Meanwhile, the content of dichloromethane extract of the crust leather of the application example 1 is obviously lower than that of the crust leather of the application comparative example, and the yellowing-resistant grade is higher than that of the application comparative example, which shows that the organic solvent extraction resistance and the yellowing-resistant performance of the crust leather which is fatliquored by the fatliquoring agent prepared by the method are both superior to those of the crust leather which is fatliquored by the commercial fatliquoring agent.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (8)
1. The reactive fatting agent is characterized by comprising 15-45 parts by weight of chlorine-terminated triglyceride and 2-6 parts by weight of emulsifier;
wherein, the structural formula of the end-chloro triglyceride is:
wherein R is 1 Is->
、/>
、/>
Any one of R and R' is a long carbon chain with the number of carbon atoms of 5-10.
2. The reactive fatting agent according to claim 1, wherein the end-chloro triglyceride is obtained by ring-opening epoxy soybean oil with hydroxyl-containing compound and then reacting with epichlorohydrin.
3. A reactive fatliquor according to claim 2, wherein the hydroxyl-containing compound includes, but is not limited to, lactic acid, ethanolamine, diethanolamine.
4. The reactive fat liquoring agent according to claim 2, wherein the weight ratio of the epoxidized soybean oil, the hydroxyl compound and the epichlorohydrin is (2 to 4): 1 to (2.5).
5. The reactive fatliquoring agent in accordance with claim 2, wherein the epoxidized soybean oil has an epoxy value of greater than 6.
6. The reactive fatting agent according to claim 1, wherein the emulsifier is selected from tween 80 and/or span 80.
7. A process for preparing a reactive fatliquor according to any of claims 1-6, characterized by comprising the steps of:
mixing epoxidized soybean oil and a hydroxyl-containing compound at room temperature, adding a first catalyst, heating to 80-130 ℃, and reacting for 4-8 hours to obtain an epoxidized soybean oil ring-opening product;
mixing the epoxidized soybean oil ring-opening product with epichlorohydrin at room temperature, adding a second catalyst, heating to 70-90 ℃ and reacting for 6-10 hours to obtain end-chloro triglyceride; and
and mixing the end-chloride triglyceride and the emulsifier, and stirring for 1-2 hours at 70-90 ℃.
8. The method of claim 7, wherein the first catalyst is selected from any one or more of tetrabutylammonium bromide, triphenylphosphine, zinc chloride;
the second catalyst is selected from triphenylphosphine and/or boron trifluoride diethyl etherate.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101864499A (en) * | 2010-06-17 | 2010-10-20 | 陕西科技大学 | Preparation method of asymmetric Gemini type fat liquor |
| CN107326125A (en) * | 2017-08-09 | 2017-11-07 | 赞宇科技集团股份有限公司 | A kind of antimicrobial form leather fat and its production technology |
| CN111349366A (en) * | 2020-04-24 | 2020-06-30 | 中山大学 | UV-LED inkjet ink for PVC leather printing and preparation method thereof |
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|---|---|---|---|---|
| JPS4819922B1 (en) * | 1970-09-10 | 1973-06-18 | ||
| US4348201A (en) * | 1979-05-11 | 1982-09-07 | Seitetsu Kagaku Co., Ltd. | Tanning process and tanning compositions |
| DE3335845A1 (en) * | 1983-10-03 | 1985-04-11 | Henkel KGaA, 4000 Düsseldorf | LUBRICANT FOR LEATHER AND FUR |
| CN101285107B (en) * | 2008-04-07 | 2011-02-16 | 温州大学 | Composite sulfited vegetable oil leather fat-liquoring agent and method for preparing same |
| CN101948714B (en) * | 2010-09-13 | 2012-05-30 | 四川亭江新材料股份有限公司 | Method for preparing cation synthetic sperm oil fat liquor |
| CN102757528B (en) * | 2012-06-21 | 2014-02-05 | 陕西科技大学 | Preparation method of amphoteric retanning fatliquor |
| CN105296688B (en) * | 2015-11-16 | 2018-04-17 | 浙江赞宇科技股份有限公司 | A kind of preparation method of leather fat |
| CN107794318B (en) * | 2017-11-27 | 2020-07-10 | 上海金狮化工有限公司 | Fur fatting agent, formula and preparation method thereof |
| CN112941249B (en) * | 2021-02-20 | 2022-05-24 | 四川大学 | Melamine resin retanning agent and preparation method thereof |
| CN114086390B (en) * | 2021-12-08 | 2023-03-10 | 四川大学 | Epoxidized soybean oil modified collagen fiber and preparation method and application thereof |
-
2022
- 2022-08-11 CN CN202210963034.5A patent/CN115404289B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101864499A (en) * | 2010-06-17 | 2010-10-20 | 陕西科技大学 | Preparation method of asymmetric Gemini type fat liquor |
| CN107326125A (en) * | 2017-08-09 | 2017-11-07 | 赞宇科技集团股份有限公司 | A kind of antimicrobial form leather fat and its production technology |
| CN111349366A (en) * | 2020-04-24 | 2020-06-30 | 中山大学 | UV-LED inkjet ink for PVC leather printing and preparation method thereof |
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